US5066713A - Process for the preparation of aqueous, radiation-curable urethaneacrylate dispersions - Google Patents

Process for the preparation of aqueous, radiation-curable urethaneacrylate dispersions Download PDF

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Publication number
US5066713A
US5066713A US07/502,692 US50269290A US5066713A US 5066713 A US5066713 A US 5066713A US 50269290 A US50269290 A US 50269290A US 5066713 A US5066713 A US 5066713A
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Prior art keywords
nco
cooh
acrylate
weight
anhydride
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Expired - Fee Related
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US07/502,692
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English (en)
Inventor
Werner Flakus
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Huels AG
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Huels AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/68—Unsaturated polyesters

Definitions

  • the present invention relates to a process for the preparation of aqueous, radiation-curable urethane-acrylate dispersions, in the absence of solvents; the dispersions prepared by this process; and cured films of these dispersions.
  • Radiation-curable dispersions have been developed in recent years. Their development has resulted from the further development of emulsions initially cured merely by physical means in the direction of systems which are thermally or chemically post-cured. Now, films formed, for example, from unsaturated, aqueous dispersions can be cured and polymerized using UV, laser or electron beam curing in a few seconds or fractions of a second.
  • Radiation-curable, aqueous polyurethane dispersions as described, for example, in DE-A-3,526,016 have a long shelf life, extending over several years.
  • the cured films have interesting properties when applied to sheet steel and are resistant to solvents.
  • the process described above for the preparation of such dispersions is unsatisfactory. Not only the reaction time and the reaction volume, but also the consumption of solvent and energy are considerable.
  • the urethane-acrylate ionomers which are formed are known to be thermally and chemically sensitive, i.e., subject to premature polymerization during prepolymer formation or at least to undergoing gradual changes on standing.
  • one object of the present invention is to provide a simplified process for preparing aqueous, radiation-curable, urethane-acrylate dispersions in the absence of solvent, which yields dispersions and cured films which conform to the highest quality requirements, and the dispersions and cured films thus-obtained.
  • the present invention therefore relates to a process for the preparation of aqueous, radiation-curable, urethane-acrylate dispersions, in which isophorone diisocyanate is initially reacted with a hydroxyacrylate at 25° C. to 50° C. in a ratio of equivalents of NCO to OH of 3:1 to 5:1 with the formation of NCO-containing urethane-acrylates, and then the mixture is further reacted with COOH-containing ester polyols, prepared from polyols and dicarboxylic anhydrides, in the absence of solvents at 50° C. to 100° C. with the formation of substantially NCO-free, COOH-containing urethane-acrylates and the mixture is subsequently emulsified at 85° C. to 95° C. using aqueous solutions of bases.
  • COOH-containing ester polyols are those made from polyols and trimethyladipic anhydride.
  • urethane formation is, among other things, considerably retarded in the presence of acidic groups such as --COOH.
  • acidic groups such as --COOH.
  • the final result is a prepolymer low in NCO groups, having an NCO content of about 0.2%.
  • the addition of dilute NaOH, or tertiary amines, and residual proportions of water initially causes a wetting or organic and aqueous components, but finally results in a tacky resin which contains water but is not water-thinnable. Since, in a solution of acetone, DMPA forms prepolymers with COOH terminal groups, albeit after long reaction times, which with bases give usable emulsions, it can be inferred that at relatively high temperatures DMPA enters into side reactions of various kinds.
  • the process according to the present invention enables aqueous, radiation-curable, polyurethane emulsions to be expediently and reproducibly prepared without side reactions or malfunctions at 90° C. to 100° C. and in the absence of an organic auxiliary solvent.
  • isophorone diisocyanate as starting material is initially reacted with a hydroxyacrylate, such as 2-hydroxyethyl acrylate, i.e., partially acrylated to form component (A).
  • a hydroxyacrylate such as 2-hydroxyethyl acrylate
  • component (A) is carried out at a temperature of 25° C. to 50° C., preferably 30° C. to 45° C., and the ratio of the NCO groups of the isophorone diisocyanate to the OH groups of the hydroxyacrylate is suitably 3:1 to 5:1.
  • a polyol such as trimethylolpropane, butanediol, polyetherdiols and the like are melted with the addition of a dicarboxylic anhydride, such as 2,2,4(2,4,4)-trimethyladipic anhydride (TMAA) until the homogeneous melt has reached about 90° C. to form component (B).
  • TMAA 2,2,4(2,4,4)-trimethyladipic anhydride
  • component (B) 2,2,4(2,4,4)-trimethyladipic anhydride
  • TMAA 2,2,4(2,4,4)-trimethyladipic anhydride
  • the anhydride and the polyol are reacted in relative amounts such that the ratio of OH groups in the polyol and the anhydride groups is from 7:1 to 11:1, preferably 8:1 to 10:1.
  • the melt at a temperature of about 90° C. is advantageously cooled to about 50° C. and introduced as component (B) into the preliminary mixture (A) at a rate depending on the heat of reaction, such that the reaction mixture (A) gradually is heated to a temperature of from 50° C. to 100° C., preferably from 60° C. to 95° C.
  • the viscous prepolymer melt can be stirred in glass vessels with glass stirrers at 95° C. (high speed mixers are thus not required).
  • Component (B) is added to Component (A) in an amount sufficient to obtain a prepolymer which is substantially free from NCO groups or has a low content of NCO groups (NCO ⁇ 0.2% by weight, preferably ⁇ 0.1% by weight) but which still has a content of 1 to 2% by weight, preferably 1.2 to 1.8% by weight of COOH relative to the solids.
  • dilute sodium hydroxide solution is initially introduced and then residual hot water at 85° C. to 95° C., preferably 85° C. to 90° C., with stirring. Cooling down leaves a fine-particled, bluish dispersion with a long shelf life, which after drying by physical means and radiation-curing gives high gloss films.
  • the properties of the dispersions prepared according to the present invention when applied as a film to sheet steel are equivalent to the systems prepared from a solution in acetone.
  • the COOH-containing ester polyols may be reaction products of (a) polyol mixtures of, e.g., trimethylolpropane, aliphatic diols such as ethylene glycol and homologous such as polyether polyols with (b) dicarboxylic anhydrides, such as trimethyladipic anhydride (e.g., technical grade TMAA), maleic anhydride or succinic anhydride, preferably TMAA.
  • TMAA trimethyladipic anhydride
  • maleic anhydride or succinic anhydride preferably TMAA
  • the hydroxyacrylate may be any suitable hydroxy-lower alkyl acrylate.
  • 2-Hydroxyethyl acrylate is a particularly suitable hydroxyacrylate.
  • Bases used for neutralizing and emulsifying the COO-containing prepolymers are NaOH, KOH, LiOH, NH 4 OH and/or tertiary amines such as triethylamine or dimethylaminoethanol, preferably NaOH.
  • Trimethyladipic anhydride is a liquid anhydride of low viscosity which is formed by the thermal elimination of water from trimethyladipic acid with ring formation.
  • the industrial product contains approximately equal proportions of the 2,2,4- and 2,4,4-methyl isomers.
  • the acids and corresponding anhydrides are shown below. ##STR4##
  • anhydrides form emulsions having a low solids content and require a large amount of dilution with water and/or impair the shelf life of the emulsions.
  • the time required for preparing the emulsions is reduced from about 20 hours to 7 hours (see, e.g., Examples 1 and 4);
  • Alkali-resistant coatings are produced from the emulsions prepared according to the present invention after radiation-curing.
  • the coatings pass the so-called washing liquor test (exposure to 4% strength NaOH at 80° C. for 3 hours without being affected).
  • washing liquor test exposure to 4% strength NaOH at 80° C. for 3 hours without being affected.
  • Many conventional anionic dispersions do not meet this standard;
  • the shelf life of the emulsions prepared according to the invention is excellent and the properties of the emulsions applied to sheet steel are of a high standard;
  • Comparative Example 1 (Conventional Process: Method of operation employing a solvent)
  • DMPA Dimethylolpropionic acid
  • Viscosity of the dispersion Ford cup No. 4 (16 sec).
  • the preliminary mixture of ingredients as described in Example 4 is processed until a resin is formed having a NCO content of 24.9% to 25.9% by weight (A). Then 1,585.6 g of reaction product (B) described below is introduced into the preliminary mixture (A) and the reaction temperature is brought to 90° C. to 100° C. in accordance with the viscosity and heat of reaction.
  • Viscosity of the dispersion Ford cup No. 4 (25 sec).
  • the preliminary mixture of ingredients as described in Example 4 are processed until a resin is formed having a NCO content of 24.9% to 25.9% by weight (A). Then 1,587.6 g of reaction product (B) described below are introduced into the preliminary mixture (A) and the reaction temperature is brought to 90° C. to 100° C. in accordance with the viscosity and heat of reaction.
  • Viscosity of the dispersion Ford cup No. 4 (26 sec).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
US07/502,692 1989-05-19 1990-04-02 Process for the preparation of aqueous, radiation-curable urethaneacrylate dispersions Expired - Fee Related US5066713A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3916340A DE3916340A1 (de) 1989-05-19 1989-05-19 Verfahren zur herstellung waessriger, strahlenhaertbarer urethanacrylatdispersionen
DE3916340 1989-05-19

Publications (1)

Publication Number Publication Date
US5066713A true US5066713A (en) 1991-11-19

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Family Applications (1)

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Country Status (7)

Country Link
US (1) US5066713A (fr)
EP (1) EP0399160B1 (fr)
JP (1) JPH039918A (fr)
AT (1) ATE105309T1 (fr)
CA (1) CA2017013A1 (fr)
DE (2) DE3916340A1 (fr)
ES (1) ES2052090T3 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1013693A1 (fr) * 1996-08-16 2000-06-28 Inolex Investment Corporation Polyol polymère avec fonctionalité acidique, polyuréthanes et leur procédé de production
US6103822A (en) * 1996-08-16 2000-08-15 Inolex Investment Corporation Polymeric acid functional polyols, polyurethanes and methods for making same
US6335381B1 (en) * 1998-04-23 2002-01-01 Bayer Aktiengesellschaft Aqueous coating compositions containing urethane (meth)acylates having UV-hardening isocyanate groups
US20040143056A1 (en) * 2002-10-25 2004-07-22 Samsung Electronics Co., Ltd Overcoating composition and organic photoreceptor using the same
EP1707600A1 (fr) * 2005-03-31 2006-10-04 Cytec Surface Specialties Austria GmbH Composition aqueuse d'un liant durcissable par irradiation
CN102851987A (zh) * 2012-10-11 2013-01-02 北京理工大学 一种超支化水性聚氨酯涂层剂
US12227614B2 (en) 2019-12-17 2025-02-18 Covestro Deutschland Ag Process for preparing polyoxyalkylene polyester polyols

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4106121A1 (de) * 1991-02-27 1992-09-03 Bayer Ag Hydrophile, olefinisch ungesaettigte polyurethane und ihre verwendung als reaktive emulgatoren
DE4119331A1 (de) * 1991-06-12 1992-12-17 Huels Chemische Werke Ag Verfahren zur herstellung waessriger, strahlenhaertender, anionischer urethanharnstoffacrylatdispersionen
US5254611A (en) * 1992-06-30 1993-10-19 Henkel Corporation Water dispersable urethane acrylate oligomer
JP3486234B2 (ja) * 1993-12-09 2004-01-13 ペンタックス株式会社 複写用変倍光学系
JPH0894930A (ja) * 1994-09-21 1996-04-12 Minolta Co Ltd 複写用変倍レンズ系
EP2617748A1 (fr) 2012-01-23 2013-07-24 Basf Se Polyesters polyols et leur procédé de fabrication

Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929929A (en) * 1973-05-29 1975-12-30 Ici America Inc Vinyl urethane resins
US4094842A (en) * 1975-09-26 1978-06-13 Bayer Aktiengesellschaft Dispersing solid polyurethane prepolymers into water
US4123423A (en) * 1976-09-18 1978-10-31 Bayer Aktiengesellschaft Process for the manufacture of plastics containing ester and/or urethane groups
US4131602A (en) * 1977-09-29 1978-12-26 Union Carbide Corporation Radiation curable acrylated polyurethane
US4133723A (en) * 1978-01-03 1979-01-09 Lord Corporation Actinic radiation-curable formulations from the reaction product of organic isocyanate, poly(alkylene oxide) polyol and an unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive hydrogen group
US4246391A (en) * 1979-06-26 1981-01-20 Union Carbide Corporation Procedure for production of lower viscosity radiation-curable acrylated urethanes
US4268426A (en) * 1979-05-07 1981-05-19 Textron, Inc. Water-dispersible urethane polymers, aqueous polymer dispersions and half-esters useful therein
US4277380A (en) * 1979-03-29 1981-07-07 Textron, Inc. Water-dispersible urethane polymers and aqueous polymer dispersions
US4312798A (en) * 1978-12-15 1982-01-26 Basf Aktiengesellschaft Polyurethane coating solutions or dispersions
US4314922A (en) * 1980-02-11 1982-02-09 Basf Aktiengesellschaft Process for the preparation of aqueous polyurethane dispersions
US4320220A (en) * 1976-07-19 1982-03-16 Vianova Kunstharz, A.G. Cathodically depositable coating compositions and process for same
US4339566A (en) * 1979-09-06 1982-07-13 Bayer Aktiengesellschaft Water-dispersible, radiation-crosslinkable binding agents from urethane acrylates, a process for their production, and the use thereof in aqueous dispersions in color painting, color printing, and textile applications
US4451636A (en) * 1981-01-16 1984-05-29 W. R. Grace & Co. Polymer composition having terminal alkene and terminal carboxyl groups
US4497932A (en) * 1982-07-01 1985-02-05 Resem, S.P.A. Aqueous dispersions of polyurethanes from oligo urethanes having unsaturated terminal groups
US4507458A (en) * 1983-04-14 1985-03-26 Takeda Chemical Industries, Ltd. Urethane acrylate compositions
US4605723A (en) * 1984-06-13 1986-08-12 Huls Aktiengesellschaft Shelf-stable, isocyanate (NCO) free urethane urea acrylate resins
US4608409A (en) * 1985-05-08 1986-08-26 Desoto, Inc. Polyacrylated oligomers in ultraviolet curable optical fiber coatings
US4711929A (en) * 1985-03-18 1987-12-08 E. I. Du Pont De Nemours And Company Acrylourethane reaction product
US4722966A (en) * 1985-07-20 1988-02-02 Huls Aktiengesellschaft Storage-stabile, radiation-hardenable, NCO-free aqueous emulsions
US4730021A (en) * 1984-06-04 1988-03-08 Polyvinyl Chemie Holland B.V. Process for preparing aqueous dispersions of acrylic-urethane graft copolymers
US4870152A (en) * 1987-11-03 1989-09-26 Bayer Aktiengesellschaft Process for the production of compounds containing isocyanurate groups and olefinic double bonds and their use as binders
US4874799A (en) * 1985-05-17 1989-10-17 M&T Chemicals Inc. Aqueous akaline developable, UV curable urethane acrylate compounds and compositions useful for forming liquid 100 percent solids, solvent-free solder mask coatings
US4914173A (en) * 1986-12-06 1990-04-03 Smith And Nephew Associate Companies Plc Adhesives, their preparation and use
US4920157A (en) * 1987-03-26 1990-04-24 Basf Aktiengesellschaft Radiation-curable contact adhesives based on polyurethane acrylates
US5003026A (en) * 1989-06-22 1991-03-26 Armstrong World Industries, Inc. UV curable no-wax coating

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3676054D1 (de) * 1985-05-17 1991-01-17 Atochem North America Durch waessriges alkali entwickelbare, uv-haertbare urethanacrylatverbindungen und zusammensetzungen, die zur herstellung von beschichtung fuer loetmasken geeignet sind.

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929929A (en) * 1973-05-29 1975-12-30 Ici America Inc Vinyl urethane resins
US4094842A (en) * 1975-09-26 1978-06-13 Bayer Aktiengesellschaft Dispersing solid polyurethane prepolymers into water
US4320220A (en) * 1976-07-19 1982-03-16 Vianova Kunstharz, A.G. Cathodically depositable coating compositions and process for same
US4123423A (en) * 1976-09-18 1978-10-31 Bayer Aktiengesellschaft Process for the manufacture of plastics containing ester and/or urethane groups
US4131602A (en) * 1977-09-29 1978-12-26 Union Carbide Corporation Radiation curable acrylated polyurethane
US4133723A (en) * 1978-01-03 1979-01-09 Lord Corporation Actinic radiation-curable formulations from the reaction product of organic isocyanate, poly(alkylene oxide) polyol and an unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive hydrogen group
US4312798A (en) * 1978-12-15 1982-01-26 Basf Aktiengesellschaft Polyurethane coating solutions or dispersions
US4277380A (en) * 1979-03-29 1981-07-07 Textron, Inc. Water-dispersible urethane polymers and aqueous polymer dispersions
US4268426A (en) * 1979-05-07 1981-05-19 Textron, Inc. Water-dispersible urethane polymers, aqueous polymer dispersions and half-esters useful therein
US4246391A (en) * 1979-06-26 1981-01-20 Union Carbide Corporation Procedure for production of lower viscosity radiation-curable acrylated urethanes
US4339566A (en) * 1979-09-06 1982-07-13 Bayer Aktiengesellschaft Water-dispersible, radiation-crosslinkable binding agents from urethane acrylates, a process for their production, and the use thereof in aqueous dispersions in color painting, color printing, and textile applications
US4314922A (en) * 1980-02-11 1982-02-09 Basf Aktiengesellschaft Process for the preparation of aqueous polyurethane dispersions
US4451636A (en) * 1981-01-16 1984-05-29 W. R. Grace & Co. Polymer composition having terminal alkene and terminal carboxyl groups
US4497932A (en) * 1982-07-01 1985-02-05 Resem, S.P.A. Aqueous dispersions of polyurethanes from oligo urethanes having unsaturated terminal groups
US4507458A (en) * 1983-04-14 1985-03-26 Takeda Chemical Industries, Ltd. Urethane acrylate compositions
US4730021A (en) * 1984-06-04 1988-03-08 Polyvinyl Chemie Holland B.V. Process for preparing aqueous dispersions of acrylic-urethane graft copolymers
US4605723A (en) * 1984-06-13 1986-08-12 Huls Aktiengesellschaft Shelf-stable, isocyanate (NCO) free urethane urea acrylate resins
US4711929A (en) * 1985-03-18 1987-12-08 E. I. Du Pont De Nemours And Company Acrylourethane reaction product
US4608409A (en) * 1985-05-08 1986-08-26 Desoto, Inc. Polyacrylated oligomers in ultraviolet curable optical fiber coatings
US4874799A (en) * 1985-05-17 1989-10-17 M&T Chemicals Inc. Aqueous akaline developable, UV curable urethane acrylate compounds and compositions useful for forming liquid 100 percent solids, solvent-free solder mask coatings
US4722966A (en) * 1985-07-20 1988-02-02 Huls Aktiengesellschaft Storage-stabile, radiation-hardenable, NCO-free aqueous emulsions
US4914173A (en) * 1986-12-06 1990-04-03 Smith And Nephew Associate Companies Plc Adhesives, their preparation and use
US4920157A (en) * 1987-03-26 1990-04-24 Basf Aktiengesellschaft Radiation-curable contact adhesives based on polyurethane acrylates
US4870152A (en) * 1987-11-03 1989-09-26 Bayer Aktiengesellschaft Process for the production of compounds containing isocyanurate groups and olefinic double bonds and their use as binders
US5003026A (en) * 1989-06-22 1991-03-26 Armstrong World Industries, Inc. UV curable no-wax coating

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1013693A1 (fr) * 1996-08-16 2000-06-28 Inolex Investment Corporation Polyol polymère avec fonctionalité acidique, polyuréthanes et leur procédé de production
US6103822A (en) * 1996-08-16 2000-08-15 Inolex Investment Corporation Polymeric acid functional polyols, polyurethanes and methods for making same
US6335381B1 (en) * 1998-04-23 2002-01-01 Bayer Aktiengesellschaft Aqueous coating compositions containing urethane (meth)acylates having UV-hardening isocyanate groups
US20040143056A1 (en) * 2002-10-25 2004-07-22 Samsung Electronics Co., Ltd Overcoating composition and organic photoreceptor using the same
EP1707600A1 (fr) * 2005-03-31 2006-10-04 Cytec Surface Specialties Austria GmbH Composition aqueuse d'un liant durcissable par irradiation
WO2006103026A3 (fr) * 2005-03-31 2007-08-23 Cytec Surface Specialties At Composition de liant aqueuse sechee par rayonnements
CN102851987A (zh) * 2012-10-11 2013-01-02 北京理工大学 一种超支化水性聚氨酯涂层剂
CN102851987B (zh) * 2012-10-11 2015-01-07 北京理工大学 一种超支化水性聚氨酯涂层剂
US12227614B2 (en) 2019-12-17 2025-02-18 Covestro Deutschland Ag Process for preparing polyoxyalkylene polyester polyols

Also Published As

Publication number Publication date
EP0399160B1 (fr) 1994-05-04
EP0399160A1 (fr) 1990-11-28
DE59005583D1 (de) 1994-06-09
CA2017013A1 (fr) 1990-11-19
JPH039918A (ja) 1991-01-17
DE3916340A1 (de) 1990-11-22
ATE105309T1 (de) 1994-05-15
ES2052090T3 (es) 1994-07-01

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